Rovers were the better side overall but could not stick the ball in the net and were punished when big defender Neill Collins headed home nine minutes from time.
However, Collins was fortunate to still be on the pitch at that stage of the game.
The 25-year-old Scotsman was named among the substitutes but got his chance when regular centre-back Michael Mancienne was injured in the warm up.
Collins had another stroke of luck when he was only booked for bringing down Lewis Guy in the 62nd minute when the fleet-footed Rovers striker was clean through on goal.
The Wolves man was the last defender and could have been shown the red card but he made the most of his good fortune to head home the winner in the 81st minute.
Michael Kightly delivered a curling free-kick from the left and Collins rose high to head home in fine style.
It was cruel luck on Doncaster and typical of a season in which they have lost ten games by the odd goal.
They played the better football after the game settled down following a hectic start and Paul Heffernan hammered a shot from just inside the box that smacked against the crossbar in the 26th minute.
Wolves seldom threatened in the first half apart from an extraordinary incident in the 38th minute when Andy Keogh hit the woodwork twice and Stephen Ward had a shot cleared off the line.
Home keeper Neil Sullivan also parried another attempt from Richard Stearman in between an amazing goalmouth melee.
Play was more even after the interval but Doncaster were unfortunate not to be awarded a penalty when keeper Wayne Hennessey pushed Guy in the back in the 53rd minute before Collins brought down Guy again nine minutes later.
Collins' goal knocked the stuffing out of Rovers and they rarely went close to snatching the equaliser they deserved.